Water-insoluble mono-azo dyestuffs containing a cinnamoylamine coupling component

ABSTRACT

DYESTUFFS, CONTAINING NO ACID GROUPS, OF THE FORMULA:   1-(A-N=N-),2-(PHENYL-CH=CH-CO-NH-),4-(R1-N(-R2)-),5-X-   BENZENE   IN WHICH A REPRESENTS THE RESIDUE OF A DIAZOTISABLE AMINE, R1 AND R2 EACH REPRESENT AN ALKYL GROUP HAVING UP TO FOUR CARBON TOMS AND X REPRESENTS A HYDROGEN ATOM OR A METHYL, ETHYL, METHOXY OR ETHOXY GROUP, COUPLING COMPOUNDS OF THE FORMULA:   1-(PHENYL-CH=CH-CO-NH-),4-X,5-(R1-N(-R2)-)BENZENE   IN WHICH R1, R2 AND X HAVE THE MEANINGS GIVE ABOVE. THE DYESTUFFS ARE OF PARTICULAR INTEREST FOR THE COLOURATION OF HYDROPHOBIC FIBERS AND PROCESSES FOR THE PREPARATION OF THE DYESTUFFS AND THE COUPLING COMPOUNDS ARE DISCLOSED.

United States Patent Int. Cl. ciwd 29/00 US. Cl. 260-2071 5 ClaimsABSTRACT OF THE DISCLOSURE Dyestuffs, containing no acid groups, of theformula:

in which A represents the residue of a diazotisable amine, R and R eachrepresent an alkyl group having up to four carbon atoms and X representsa hydrogen atom or a methyl, ethyl, methoxy or ethoxy group.

Coupling compounds of the formula:

1 2 CH=CHC OHN in which R R and X have the meanings given above.

The dyestuffs are of particular interest for the colouration ofhydrophobic fibres and processes for the preparation of the dyestuffsand the coupling compounds are disclosed.

The present invention relates to new monoand disazo dyestuffs which areof particular interest for the colouration of hydrophobic fibres.

These new dyestuffs, containing no acid groups, may be presented by thegeneral formula:

R2 11111 C O in which R represents the residue of a diazotisable amine,R and R each represent an alkyl group having up to four carbon atoms andX represents a hydrogen atom or a methyl, ethyl, methoxy or ethoxygroup.

The dyestuffs of Formula I may be prepared for example by coupling inacid medium the diazo derivative of an aromatic or heterocyclicdiazotisable amine ANH with a coupling compound of the general formula:

3,644,329 Patented Feb. 22, 1972 ice -on=ono 0111 1 in which A, R R andX have the same significance as above.

The diazotisable amine ANH may belong to a variety of series, such asfor example the following: benzene, benzene-azo-benzene, naphthalene,naphthalene-azo-benzene, thiazole, benzothiazole, thiadiazole, orthiophene. In the case of heterocyclic amines, the amino function may beeither on the heterocyclic ring or on the benzene ring. Thediazotisation of the amine may be effected for example by knownprocesses using sodium nitrate or acid nitrosyl sulphate.

The coupling compounds of Formula II are new products. They may beprepared, for example by the action of cinnamoyl chloride in an inertsolvent or diluent on an amine of the general formula:

to an alkylation treatment.

In view of their tinctorial applications, it is advantageously for thedyestuffs obtained to be in a finely divided state. For this reason, thedyestuffs according to the invention are preferably pre-dispersed andprovided in the form of a paste or powder. This form may be obtained bymixing the dyestuffs in paste form with dispersing agents, and possiblywith inert diluents. If desired the mixing may be followed by drying andgrinding. The dyestuffs thus treated can then be used for dyeing in along or short bath, in foularding or in printing.

Examples of dispersing agents which may be used are the productsresulting from the condensation of naphthalenesulphonic acids withformaldehyde, especially the dinaphthylmethane disulphonates, esters ofsulphonated succinic acid, alkali metal salts of sulphuric esters offatty alcohols, for example sodium lauryl-sulphate, lignosulphonates,soap, alkali metal salts of the sulphuric esters of monoglycerides offatty acids or the products obtained by the condensation of the cresolswith formaldehyde and naphthol-sulphonic acids, condensation products of4,4'-dihydroxy-diphenylsulphone with formaldehyde and alkali metalbisulphites.

The dyeing of polyester fibres may be carried out in the presence of acarrier at a temperature from C. to C. inclusive or without a carrierunder pressure at a temperature from 100 C. and C. inclusive.

The fibres can also be foularded or printed with aque ous dispersions ofthe new dyestuffs, the impregnation obtained being then fixed at atemperature from between 140 C. to 230 C. inclusive for example by meansof steam, air or by contact with a heated surface. The range oftemperature from 180 C to 200 C. inclusive is particularly favourable,since the dyestuffs diffuse rapidly into the polyester fibres and do notsublime even if the action of these high temperatures is prolonged. Thisenables fouling of the dyeing apparatus tobe avoided.

Cellulose diacetate is preferably dyed by exhaustion at a temperaturefrom 65 C. to 85 C. inclusive and cellulose triacetate and polyamidefibres are preferably dyed at a temperature up to 115 C. The mostfavourable pH region is between 2 and 9 inclusive and especially between4 and 8 inclusive. Like the polyester fibres, the triacetate andpolyamide fibres can be foularded or printed with an aqueous suspensionof the new dyestufls with subsequent fixing of the impregnation obtainedat a temperature from 140 C. to 210 C. inclusive.

During foularding or printing, the usual thickeners may be used, forexample modified or unmodified natural products, such as alginates,crystalline gum, carob, gum tragacanth, carboxymethyl-cellulose,hydroxyethylcellulose, starch, or synthetic products such as polyacrylicamides or polyvinyl alcohols.

The shades thus obtained are remarkably fast to thermal fixation,sublimation, creasing, combustion gases, overdyeing, dry cleaning,chlorine and wet tests, for example water, washing and sweat. Thereserve of the natural fibres, especially of wool and cotton, and thedischargeability are good. The fastness to light is remarkable even withlight shades, so that the new dyestuffs are very suitable for theproduction of fashion shades. The dyestufifs resist boiling andreduction at temperatures from 80 C. to 220 C. inclusive. This stabilityis not altered by the bath ratio nor by the presence of dyeingaccelerators.

The new dyestuffs can also be used for dyeing polyolefine fibres, andfibres based on polymers or copolymers of acrylonitrile or based onpolyvinyl derivatives.

The dyestuffs of Formula I can further be used for the bulk colourationof varnishes, oils, synthetic resins and synthetic fibres spun fromtheir solutions in organic solvents.

Compared with similar dyestuffs of the formula:

Ra NH-acyl such as N-formylated and N-acetylated derivatives, thedyestuffs according to the invention has a distinctly improved fastnessto sublimation.

The invention is illustrated by, but not limited to, the followingexamples, in which the parts are parts by weight unless the contrary isindicated.

EXAMPLE 1 408 parts of freshly distilled (B.P. 112 C. under 0.7 mm.)N,N-dimethyl-metaphenylenediamine are added to 900 parts of xylene then450 parts of freshly distilled N,N- diethyl-aniline, and finally, insmall portions, 500 parts of cinnamoyl chloride are added. Thetemperature rises spontaneously to 115 C. The reaction product is keptfor 2 hours under gentle reflux, then left to cool. The thick mass isrun into 4500 parts of water at C. with vigorous strring, and themixture is filtered, and the solid again made into a paste in 2000 partsof hot water, the paste is acidified until a violet colouration isobtained on Congo red paper, then filtered, and the solid dried. 785parts of N,N dimethyl-N'-cinnamoyl-metaphenylene-diamine are obtained.Melting point: 182-183" C.

EXAMPLE 2 20.8 parts of 2-amino-3,S-dinitro-benzonitrile are made into apaste in 50 parts of 66 B. sulphuric acid. The mixture is cooled to 0 C.and parts of acid nitrosyl sulphate (prepared from 6.9 parts of sodiumnitrite) are run in, While the temperature is maintained at between 0 C.and 5 C. After stirring for some hours, 50 parts of acetic acid and then26 parts of N,N-dimethy1-N- cinnamoylmetaphenylenediamine dissolved in100 parts of acetic acid are added, while maintaining the sametemperature. The syrupy mass is run into a mixture of water and ice,filtered, and if desired again made into a paste and a dispersing agentadded to the paste, for example a cresol-formaldehyde-naphtholsulphonicacid condensation product, and ground. The dyestuffs dyes fibres ofethyleneglycol polyterephthalate and cellulose triacetate a greenishblue shade.

The following table gives additional examples of dyestuffs according tothe invention. The bases used for their preparation can be diazotised bythe conventional industrial methods, for example by means of sodiumnitrite or acid nitrosyl sulphate according to their basicity. Thecinnamoylamino group of formula is denoted by the abbreviation Nz. Theshades are those obtained on ethylene glycol polyterephthalate fibres.

carlet.

amino-2-Nz-benzene].

14 [2,4dinitro16-ehloro-benzene}(1 azo 1)-[5-methoxy-4-di- Blue.

methyl-ammo-2-Nz-benzene].

15 [2-cyano-4-n1tro-benzene1-(1 azo 1)-[5-methyl-4-dlmethyl- Blueviolet.

amino-2- z-benzene].

l6 [2-nit ro-4-methy1sulphonyl-benzene1-(1 azo 1)-[4-dimethyl- Bluishred.

ammo-Z-Nz-benzene].

l7 [lghloro-ijnitrdbenzenq-(l azo 1)-[4-dhnethylamino-2-Nz- Do.

enzene 18 [4-nitro-benzene1-(1 am 1) -[5-methyl-4-dhnethylamino-2-Scarlet.

N z-benzene].

TABLE IContiniued benzene] By coupling the diazo derivatives of theamines listed below with N ,N -dimethyl-N-cinnamoyl-1,3-phenylencdiamine, other dyestuffs of Formula I areobtained.

TABLE II Ex- Shade on ample Amines polyester 294-methylsulphonyl-l-naphthylamine Red brown. 30 2-amin0-5-nitro-thiazoleReddish blue. 31 -nitro-2-amh1o-1,3,4-thiadiazole Ru y. 322-amino-3-nitro-5-acety1-thiophene.. Green blue 332-amino-6-nitro-benzothiazole- Ruby. 34. 2-amino-6-eyano-benzothiazole.Bluish red 35.. 2-amino4,G-dinltro-benzothiazole. Green blue. 36-2-an11ino-4-nitro-6-methylsulphonyl-benzothia- Blue violet.

Z0 e. 37 2-am11no-6-chloromethylsulphonyl-benzothia- Ruby.

zo e. 38...... Z-amino-6-thiocyanato-benzothiazole- Do. 39..3-phenyl-5-amino-1,2,4-thiadiazole-... Do. 40.- 4-amino-azobenzene Red.41 4-amino-2-methoxy-azobenzene.. Blnish red. 424-amino-3-chloro-azobenzene Do. 43 4-nitro-Z-methyl-l amino-azo-benzeneBed. 44 l-phenylazo-4-amlno-naphthalene Red.

EXAMPLE 45 A fabric of ethylene glycol polyterephthalate is impregnatedby foularding with a bath which contains, per 1000 parts by volume, 9.0parts of the dyestuff obtained in Example 2, 0.5 part of a polyglycolether of oleyl alcohol, 1.5 parts of a polyacrylic amide and the amountof water necessary to make up to 1000 parts. After drying, the fabric issubjected to thermal fixation for 1 minute at 200 C. and then to areducing treatment by sodium dithionite. A greenish blue shade isobtained which is fast to light and sublimation.

EXAMPLE 46 A fabric of ethyleneglycol polyterephthalate is printed witha printing paste which contains, per 1000 parts, parts of the dyestuffdescribed in Example 3, 150 parts of the sodium salt of a sulphonatedcastor oil, 600 parts of a thickener and 230 parts of water. Afterdrying, the fabric is subjected to thermal fixation for 1 minute at 200C. and then to a reducing treatment. A blue shade having good generalfastness is obtained.

EXAMPLE 47 100 parts of a cellulose triacetate fabric are introduced at60-70 C. into a dyebath of 3000 parts by volume, which contains 1 partof the dyestuff described in Example 18 and 15 parts of o-phenylphenol.The bath is brought to the boil in a period of half an hour and thedyeing is continued at the boil for 1 hour. After finishing treatment, ascarlet shade of good general fastness is obtained.

We claim:

1. A monoazo dyestuif of the formula:

wherein R and R each represent an alkyl group having up to four carbonatoms, X is hydrogen, methyl, ethyl, methoxy or ethoxy, U is hydrogen,chlorine, cyano, nitro, methylsulfonyl or methoxycarbonyl, V ishydrogen, chlorine, cyano, nitro, methylsulfonyl, ethoxycarbonyl,acetyl, trifiuoromethyl, thiocyanato, chloromethylsulfonyl,dimethylaminosulfonyl or cyclohexylaminocarbonyl and W is H, chlorine,bromine or nitro.

2. [2-cyano 4,6 dinitro benzene1-(1 azo1)-[2-cinnamoylamino-4-dimethylamino-benzene] 3. [4-nitro 2 cyano 6chloro-benzene1-(1 azo 1)- [Z-cinnamoylamino-4-dirnethylamino-benzene]4. [4 nitro 2 cyano benzeneJ-(l azo1)-[2-cinnarnoylamino-4-N-ethyl-N-methylamino-benzene] 5. [2 nitro 4chloro benZene]-(l azo 1)-[2-cinnamoylamino-4-dimethylamino-b enzene]References Cited FOREIGN PATENTS LEWIS GOTTS, Primary Examiner D. M.PAPUGlA, Assistant Examiner US. Cl. X.R.

